New vat dyestuff isomers



Patented Nov. 22, 1932 U ITED mam i inrm qmiffiievnsn na e AssIeNfons to ennnmnmmnn wonxs, moaornnw roux; N: n I;

came aman on sm wma v NEW vm'n nsrurr rsonfins No Drawing. Application filed Apri1'4, 1930, Serial No. 441,714, and in Germany May 10, 1929.

In the U. S. P. 1,588,45Lthere is described a rprocess which comprises condensing a 1.4.5.8-naphthalenetetra-carboxylic ac d compound with; an orthodiamine compound.

The products thus obtainable are valuable dyestuffs, althoughthey are not of uniform constitution, but rather represent mixtures of isomeric dyestuffs; When condensing, for instance; 1.4.5.8-naphthalenetetra carboxylic 1 0 acid with ortho-phenylenediamine a mixture of the. two isomeric dyestuffs of the following formulae: 1

tuted ortho=pl1enylenediamine with 1. 4.5.8- naphthalenetetra-carboxylic acid. in many cases the same holds true, i. e. there is likewise obtained a mixture of the two isomers. The present invention relates toa' process of separating the dyestuff mixtures obtainable according to' UD'S. P. 1,588,451 into their two components. Another object of our invention is the purified dyestuffs obtainable V 4.0 according to our newprocess.

however, thisrplain method is not suflicient I quantityof'mono chloro-atic acid as i's sufiif- 'cientto' dissolve the greater part'of the dyet'ufl'mixture by which step; of our processithe more easily soluble component is completely going into "solution andsimultaneously a 'ponent isdissolved, whereas'ias the residue there r mains the reat r, pare 85- 115 ess, as ilysoluhle isemerie dyestulf. In rde pb complete 'the'separ'ation'weinake use of ou'r We have found that the dye/stuff mixtures obtainable) according to U, SIP. 1,588,451 can be separated into their components by, means of inofiqchloro-acetic acid. In some cases it is possible to carry out the separation by treating the material at an elevated temperature with'sucha quantity of mono-chloro acetic acid as is necessary to dissolve the more easilysoluble component whereby the more diflicultlysoluble isomer remains in the residue and the dissolved isomer may be recovered by' diluting or coolingthe mono-- chloro-acetic acid solution. most cases,

for effecting a complete separation of the 5 isomeric dyestuffs. In these'cases we prefer toproceed as follows: 8 7

We treat'thedyestuif mixture with suc'lia smaller'paitof theless' easily soluble com as to their solubility in mono-chloro ac etic acid as itheidyestuflfs proper, add reaction mixturesuch quantity of an acid as as 118 8"stay"' 438mm d Sara-8r; the ,75 "dyestuffcomponents:l ac-i less soluble isomenc dyestufi" isthus" precipisat. 8f the mad and the sepaafidaofgth warmers is completed After this we' filt'erthe s 11*- tion from theresidue' treat' ifiltrat' as 7 well as the residue with water, whereby from the residue the one component andfromthe filtrate the other component is obtained;

We have foundthat the acid salts formed by acting upon the dyestuffs with hydrOchlo- V ric, hydrobromic. or sulfuric acid are most suitablefor the purposes of our invention.

We have furthermore found that ingeneral one part'by weight of the dyestufi mixture is to be treated with about 10 to parts of mono-chloro-acetic acid in order to I V dissolve the more easily soluble component and simultaneously a certain part of the less I; easily soluble dyestuff. We have found it preferable. tocarry out :the qtreatment with mono chloro-acetic' acid at a temperature of 1 about 7.0 C.100 C. V

obtainable-by condensing a 1.4;;5-.8,-n aphtha- .lenetetra carboxylic acid with al.2-diaminobenzene according to U, SgPatentNQ; 1,588,- 451,- are introduced into -2O01parts of melted mono-chloro-acetic acid at. a} temperature, of

dyestuif B. They have the following for- Inulae: A v I 7 -,The.following examples serve to illustrate i 7 7 the'ifinve ntionflbut they are not intended to limit it thereto, the 'partsbeiiig by Weight.

(1) 10 parts of the mixture of the isomeric dyestuffs of the following composi:

tions: V v

' I "stufi mixture dissolves to a, red solution.

After'some time, such' a quantity of concen- Qtrated" hydrochloric acid added slowly as I r is necessary to form the hydrochlorides of V lthe dyestufi components whereby the melted mass assumes alittle lightercolorationi The more difficultly soluble hydrochloride at once .begins, to crystallize. from vthe solution.

"The .aageay as'rpo dermonohydrate to aibrownish solutionLandidyes cotton from an olivevat 've'ry brilliant orange tints of excellent fastness, properties.

The red dyestufl' dissolves inconcentrated "surfuric' acid to ared-solution'and dyes cotton, from an olive vat bluish red tints of very good fastness properties.

When treating the dyestuif mixture only i with 'inono-chlorowace'tic .acid it [may like. 7

wise be separated into its components though "not completely.

2)' By replacing the process} of separat ng the dyestufi' mixtures asdescribed in Example 1 the hydrochloric"acid-by the equivalent quantity of sulfuric acid thefisparation is effected in avery similar way with formationof the sulfates." Also'by means of hydrobromides formed by causing concentrated hydrobromic 'acidto react with the solution in .monochloro acetic acid of j the dyestufi' used in Example ,1" the separation a of the mixtures'into their-components may be carried out in like manner;

-(3)' The redmixtureof the isomeric dye;

stufi's of the following compositions:

I Whenlthe P p a n"is'finished; the sol d product is filtered. by suction means. of: 'filter stone, washed with melted mono-chloroacetic acid and the residue on the vfilter aswell asthefiltrate is treated with water at, anelee 1 gvated temperature in order to obtain the separated dyestufis.'"'From the, yellowish brown i iesiduepn the filterfthere is obtained an or- 'angeldyestufl and from the'filtrate' a red obtainable by condensing a 1.4.5.8=naphtha'- lenetetra-carboxylic acid with a-4-methyl- 1.2-diaminobenzene can be separated in the same manner into its two components. The more difiicultly soluble sulfate yields an orange dyestufi of the following formula:

wherein R stands for the residue which dyes cotton from a green hydrosulfite Vat a clear orange red tint, whereas the dyestuff obtained from the filtrate which has the following formula:

wherein R stands for the residue v I andwhichobtained in a larger yield than the orange dyestufi, dyes cotton in somewhat dull reddish brown tints.

- (4:), 10 parts of the mixture of the iso meric dyestufis: of the following oomposir tions: V

" on, v

- main-thy amassing-a"iazss m ttia lenetetra-carboxylioiacid with a 4.5-dimeth yl-l.2 di aminobenzene are" dissolved partially in about 150 parts ofmelted monochloro-acetic acidand into this solution are slowly introduced at a temperature of from C. 150100? C. 4.3 parts of concentrated sulfuric acid or the equivalent quantity of hydrochloric acid. After; the melted mass is stirred for about 1 hour the precipitated 1 difficulty soluble sulfate or hydrochloride,

respectively, is filtered by suction and washed with a small quantity of melted mono-chloro-acetic acid; "From the residue on the filter there isiobtained bydeconipo'sitionwith Water a r d fi ch hasgthe following formula: y. v

and dyes cottonfrom a'green hydrosultite yat red tintsg From the deep .red filtrate there is precipitated by addition ofwatr a" dark brownish violetlprecipitate which ,rwlien it isif lte'red,hy-, suction and dried, represents ing formula: J

. dyeing. eptton from .a hydrosulfite 1vat Bordeaux red tints. f

(5) 100 parts of "the mixture Of the tionsfz:

obtainable by condensing a, 1.4.5.8-naphthalenetetra-carboxylie acid with a lQ-dia'minonaphthalene are dissolved. in about to times theirweight ofmelted mono-chloroacetic' acid'at about C. transformed into the sulfates by addition of &0 parts of con.-

' centrated sulfuric acid and stirred at a tem "peraturejd f' froin" 70 C. t0 8O-C.'unti1;the

gprecipitatien qfithe more diffibultly soluble "partfof theniixtiire is finished. The-precipi- 'ta te is'filtered by suction by me'ans of a filter v LCOI'diIlg to the process :ef the precedingfexam V V a From the filtrate a .stdne er'asbe'stos; The residue yielas" a violet dyestnfi ofth-e follewing formula; v

which dyes cotton from a hydresul fite'vat violet. tints of good fastne'ss properties. dyestuff of the following r u w f is obtained whieh dyes cotton frerna hydrosulfite'vat'currant tint$.

(6) B y separating inte 1ts Components 50- I r 5115 in f ples the mixture of the isomeric dyestuffs of wherein R stands for the residue 7 the following compositions: r

i. g which dyes cotton from-an olive green vat 10' brown shades. i r

(7 The red brown mixture of the iso- O meric dyestuffs of the following compositions:

a a i a 16, R NA wherein R stands forthe residue i-. v obtainable by condensing'a 1.4.5.8-naphthalenetetra-carboxylic acid or its anhydride 7 N 7 with a t-chloro-l.Q-diaminobenzene there is -;j;- g; 1'; a y obtained as difiicultly' soluble part of the mix I ture a dyestufi of thefollowing formula; wherein R stands for the residue R v v V q A v W 7 i obtainable by condensing a 1.4.5'.8-naphtha-' it a lenete'tra-carboxylic acid and a 4+bromo-1.2- I Y 0 f diaminobenzene can be separated in like manner into its components oi which the .40, l more diflicultly soluble one hasthetfollowing 105 5 R formulaz V wherein R stands for the residue 3 Y N N which dyes cotton from an olive green hydrosulfite vat scarlet tints of good fastness propj erties; The mono-chloro-acetic acid filtrate yields a dyestu-ff of the following formula:

wherem R stands, for the {res due no Z r t M and dyes cotton from an olive" green hydro- I fags i V sulfiteyat copper red tints. The more readily 13o soluble isomerobtained frorn'the filtrate has the following formula I v wherein-stand :forthe res due f; V I

y JNO: 7 c and which dyes cotton from an olive hydro- 1' sulfite vat blue grey tints, whereasthe iso'mer obtained from the mono-c'hloro-acetic acid filtrate which has the followingformula wh rein R stands for the residue 1 a a v I a y 4 v.

I V Br 7 I g and dyes cotton froman oliye g een vat brown shades. 25'- '(8) When the mixture ofthe isomeric dyestufi's of the following compositions? no.3 B. f

K y whereinR standsfor the residue .a

' '30 r 1 o I y I v noa".

I v I 4 i v dyes cotton from'an olive alkaline hydro- I y i N 7 sulfite vat grey tints. V I a V a V (9) 10 parts of theniixtureofthe isomeric 9 wherein R stands for theresidue I dyestufis of e followmg composltlonsi 45, 7 a c 31 m 7 V NO: V V

obtainable by condensing a 1.4.5.8-naphthalenetetra-carboxylic acid with a 4-nitro-L2- v v diaminobenzene is transformed into the sul- ,r

6 fates or hydrochlorides of the dyestufi comy ponents by means ofvajmono-chloro-acetic acid solution or suspensioma diflicultly'solw I v V y V ble isomer separates which has the following y Y ,7 formula: f V 7 V. '7

P55 n. V wherein R stands for the residue f i 7 7 I CH1 i, V I V I V obtainable by condensing a 1.4 .5.8-naphthalenetetra carboxylic acid" or its" anhydride "with a 't-inethoXy-1.2-di'aminobenzene,' are 7 9,

introduced in, 10-12 times their weight of melted mono-chloro-acetic acid ata'temperature of about 70 C. to 80 CQ and the whole is stirred for some time. 4.5 parts of sulfuric acid of 66 B; are then added drop by drop, stirring is continued for: some time and the sulfate of the diflicultly soluble dyestufi' com ponent which has separated is filtered by with water there is obtained from the filtrate a reddish brown dyestufi" which has the following formula:

' a oo s/ wherein R stands forthe residue bomb] and dyes cotton from an olive green alkaline hydrosulfite vat red brown tints. The monochloro-acetic acid filtrate yields a iviolet brown dyestufi of the following formula:

which dyes cotton from an olive green hydro sulfite'vat violet brown-tints of good fastness properties. r

suction at C. to C. By decomposition Both of the components yield olive vats same as the parent material.

(10) The mixtureo'f the isomeric dyestu'fis of the following compositions:

wherein R stands for the residue s 02H; obtainable by condensing a 4-ethoxy-L2- diaminobenzene and a 1.4L5.8-naphthalenetetra-carboxylic acid which is very similar to the mixture used in Example 9, can be-separated in like'manner into a red 'browndyestuff A and a violet brown dyestufiB of the following formulae:

A a VB 7 r N/ \N j 00 C wherein standsjfor the residue green (11) lOf parts of the mixture of the isomeric dyestuffs of the following compositions:

N T/ p h gyl/ wherein R'stands for the residue obtainable by condensing a 1.4.5.8-naphtha- "lenetetra carboxylic acid with a 3.5-dimethyl- 1.2-diaminobenzene, are introduced at'about 70 G. into 150 parts of melted mono-chloroacetic acid, the whole is stirred and such a quantity of sulfuric acid is added as is necessaryto form the sulfates of the dyestuf't' components. When Working up the residue and a the filtratethere are obtained two dyestufis A and'B of thefollowing formulae: 7

OH: i

olive' green hydrosulfite vat; reddish violet tints and B from a likewise olive green vat Bordeaux red tints. I

dyestufl's "of the following compositions:

wherein R stands-for the residue:

obtainable by condensing 1.4.5Q8-naphthalenetetra-carboxylic acid with a 4-chloro-5- o jbromo 1.2diaminobenzene are dispersed in some time the insoluble isomer of thedyerstuifcomponents islfiltered by suction and of which'A dyes the .cotton fiber from an (12) 10 parts of the mixture of theisomeric i about 10 times their weight ofmono-chloroe I aceticacid and conyerted into the sulfates at a temperature of between C. and C. by addition of at parts of sulfuric acid.- 5 After. Y

decomposed with lwate'r. It yields va red brown dyestufi' of the following formula :5

I 'iwhichr dy cotton from'an alkaline olive green hydrosulfite Vat red brown tints. From the mono-'chloro-acetic acid filtrate there is obtained by decomposition with water a dyestuifof'thefollowing"formulaE Y which dyes cotton froman olive green hydro e sulfite vatbrown tints. v

-(13) By cQndensing a 1.4.5.8-naPhthalenetetra-carboxylic acid or its anhydride With r4- ih a asa n b n ihem 1s obtain-eda red brown mixture of the isogmq inds es ee? meric dyestufi's of the following cornpositions:

V 5 4 5 4 1 2 1 2 I I\/N N i T o oo which mixture canbe separated by means of sulfuric acid into a larger part. of the ditficultly soluble sulfate of the dyestuffs components and into a smaller part of the sulfate which is easily going into solution. 'B'y decomposing both the sulfates with Waterthere is obtained on the one hand a 'dyestufl'of the following formula:

C1 Cl 7 V 01 which dyes cotton in scarlet tints of very goodfastness properties and on the other hand a product of the following formula which dyes cotton brownotints. Both dyest-ufis yield an olivegreen alkalinefhydrosulfl fitevat.

a, .We claim: a

1. The compounds the general fojrniulaz T 114 j I V wherein R- represents a phenylene group substituted by alkyl, :alkoxy,'halogen or nitro, or a naphthylene group tthearylene groups being bound in two adjacent positions to. the nitrogen atoms, -,the' .said products being capable ofyieldi-nga vat from ,wliich icotton is dyed ery fast tints. J

2. The compounds of the general formula;

I wherein R represents a phenylene group 9 which is substituted by atle'ast one substitu ent of the group consisting of alkyl, alkoxy, halogen and nitro the said products being capable of yielding azvat from which cotton containing two ethoxy groups in X orY -po s itidns fo rming a, iolet brownldye'stufi yielding an olive green vatfrom "which cotton is dyed fast violet-brown tints. I

4,." The; compound of the probable formula at V I gx/ wheigm 1R1 jstgirias er; the 'bii alenti m'q rant tints of goodjastness properties.

In testimony whereof we aflix our signa- WIL L IEELM'ECKERT.

OT'I- O'BBAUNSDORF. 

